CN103764588A - Neutralization-preventive high-early-strength cement composition - Google Patents
Neutralization-preventive high-early-strength cement composition Download PDFInfo
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- CN103764588A CN103764588A CN201280042423.9A CN201280042423A CN103764588A CN 103764588 A CN103764588 A CN 103764588A CN 201280042423 A CN201280042423 A CN 201280042423A CN 103764588 A CN103764588 A CN 103764588A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/16—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing anhydrite, e.g. Keene's cement
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
Provided is a neutralization-preventive high-early-strength cement composition characterized by comprising 60 to 97 wt% of a highly reactive cement and 3 to 40 wt% of an inorganic admixture, wherein the highly reactive cement is produced by adding 1.5 to 4.0 wt% of gypsum in terms of SO3 content to a highly reactive cement clinker that has a mineral composition comprising more than 70% of C3S and less than 5% of C2S as calculated in accordance with a Bouge's equation, an L. S. D. value of more than 1 and a free lime content of 0.5 to 7.5 wt%, and the inorganic admixture comprises at least one material selected from a blast furnace slag, an anhydrite, a limestone micropowder and a pozzolan substance. The neutralization-preventive high-early-strength cement composition enables the efficient use of a previously developed highly reactive cement having a high C3S content and an extremely low C2S content, and is suitable as a cement for a concrete or a mortar which is used under a low-temperature environment such as a cold region or an environment in which neutralization is likely to progress.
Description
Technical field
The present invention relates to a kind of neutralisation inhibition type short-term strength cement composition, it is is C by the mineral composition of the calculated value based on Bao lattice formula in grog
3s>70% and C
2the high reactivity cement of S<5% is as the neutralisation inhibition type short-term strength cement composition of parent, even if be and the similar material of mixed cement, also have the same intensity expression power of ordinary Portland cement and neutralisation rejection, suitable conduct is under the such low temperature environment in cold district or the concrete using under the environment of neutralisation, the cement of mortar easily occurs.
Background technology
In recent years, as preventing one of Global warming countermeasure, seek the reduction of carbon dioxide output, even if cement sectors have also been absorbed in this reduction, as cutting down one of countermeasure, focus on the mixed cement that is mixed with the inorganic admixtures such as blast-furnace slag, flyash in silicate cement, effective utilization of cement composition.
If effectively utilize these mixed cements, cement composition, not only cut down the carbonic acid gas being produced by fuel of following cement sintering, the generation that also can cut down the carbonic acid gas being caused by the decarboxylation of the Wingdale as main raw material.In addition; conventionally the mixed cement, cement composition that is mixed with the inorganic admixtures such as blast-furnace slag, flyash compared with silicate cement aspect low-heat, salt resistance (salt ?preventive property), resistance to sulfates, alkali-aggregate reaction inhibition excellence, therefore also from aspect of performance, improve demand.
But, also there are some shortcomings, as one of shortcoming, exist above-mentioned mixed cement, cement composition alkali composition (being mainly calcium component) compared with silicate cement that the situation of neutralisation less, easily occurs.For neutralisation, suppress to study, even if for example, disclose the one kind or two or more cement composition that also suppresses the corrosion of reinforcing bar under the environment of easily generation neutralisation in the group that comprises slag, blast-furnace cinder micro-powder end and flyash and the free silicate cement of choosing, blast furnace cement, pulverized fuel ash cement and slaked lime composition in patent documentation 1 always.
In addition, the good cement composition of resistance to neutralisation characteristic that one contains following (A) to (D) is disclosed in patent documentation 2: more than one the powder that (A) is selected from blast-furnace slag powder, flyash, silicon ash; (B) crushed material of sinter, described sinter contains 2CaOSiO
2and 2CaOAl
2o
3siO
2, with respect to 100 mass parts 2CaOSiO
2, 2CaOAl
2o
3siO
2+ 4CaOAl
2o
3fe
2o
3be 10～100 mass parts, 3CaOAl
2o
3content be below 20 mass parts; (C) gypsum; (D) Portland clinker crushed material.
In addition,, as one of other shortcoming in above-mentioned mixed cement, cement composition, have that intensity expression power in the short length of time is little, the bad situation of intensity expression power under such low temperature in winter particularly.
Improvement to the intensity expression power under low temperature is also studied, and for example, discloses a kind of cement composition that contains 2～10 parts by weight of cement Additives in patent documentation 3, and described cement compound is with respect to 3CaOSiO
2content is more than 60 % by weight and Brian value is 3500～7000cm
2cement 100 weight parts of/g, contain 100 weight part dehydrated gyp-s, with acid anhydrides, convert and count nitrate and/or the nitrite of Tai-Ace S 150,5～15 weight part alkali aluminate metal-salts and 20～150 weight part basic metal or alkaline-earth metal of 20～150 weight parts.
And then, as the solution that realizes intensity under above-mentioned neutralisation and above-mentioned low temperature environment and show both problems, there is patent documentation 4.Wherein disclose: containing Brian specific surface area is 6000～10000cm
2/ g and more than 70% CaO of glass rate are 40～55 quality %, Al
2o
3be 25～40 quality %, SiO
2be 10～25 quality % and Li
2o is the CaO-Al of 1～10 quality %
2o
3-SiO
2-Li
2o is that glass 100 mass parts and Brian specific surface area are 2000～8000cm
2γ-2CaOSiO of/g
2the hydraulic hydraulic cement composition of intensity expression power, resistance to vitriol resistivity and neutralisation resistivity excellence 5～300 mass parts, under low temperature environment.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2007-210850 communique
Patent documentation 2: TOHKEMY 2008-105902 communique
Patent documentation 3: No. 3549579 communique of Japanese Patent
Patent documentation 4: Japanese Patent the 4459786th communique
Summary of the invention
the problem that invention will solve
As shown in above-mentioned patent documentation 1, patent documentation 2, although known several cement composition that neutralisation suppresses of realizing, but the cement using is current silicate cement, mixed cement, therefore exist short term strength performance can not be called situation good, that can not fully guarantee the short term strength under low temperature environment.
In addition, as shown in patent documentation 3, the also cement composition of the known improvement that has realized the intensity expression power under low temperature, but be not the mixed cement of having considered that neutralisation suppresses, but and with the mixed cement of the various interpolation materials such as hardening accelerator, therefore comparatively expensive.
In patent documentation 4, disclose intensity expression power under low temperature environment and the hydraulic hydraulic cement composition of neutralisation resistivity excellence, but be the hydraulic-composition of special chemical constitution, be therefore difficult to manufacture, versatility shortcoming.
On the other hand, the inventor etc., before the present invention, have developed high C
3s and there is free lime, extremely low C
2" high reactivity cement " (with reference to Japanese Patent Application 2011-35810) of S.This cement be compared with early strength silicate cement hydration activity high, also can use the cement that is not suitable for current standard of trade waste as cement raw materials for sintering.
In view of the above problems, the object of the present invention is to provide the effective utilization that realizes above-mentioned " high reactivity cement ", even and if for also to there is the same intensity expression power of ordinary Portland cement and neutralisation rejection with the similar cement of mixed cement, thereby suitable under the such low temperature environment in cold district or the neutralisation inhibition type short-term strength cement composition of the cement of the concrete that easily occurs to use under the environment of neutralisation, mortar.
for the scheme of dealing with problems
The present invention relates to a kind of neutralisation inhibition type short-term strength cement composition, it is characterized in that, it comprises 60～97 % by weight high reactivity cement and 3～40 % by weight inorganic admixtures, and described high reactivity cement is to be C in the mineral composition of the calculated value based on Bao lattice formula (Bogue equation)
3s>70% and C
2in the high reactivity cement grog that S<5% and L.S.D. exceed 1, free lime amount is 0.5～7.5 % by weight, add with SO
3the gypsum that 1.5～4.0 % by weight are counted in conversion forms, and described inorganic admixture comprises more than one in blast-furnace slag, dehydrated gyp-, limestone micropowder end, volcanic ash material.
High reactivity cement grog refers to that hydration activity is high, utilize the peak value of the hydration electrothermal calefactive rate with conduction calorimeter of the cement of this cement clinker to be greater than the peak value of hydration electrothermal calefactive rate of the cement that has utilized the grog suitable with cement clinker and hydration thermal value more than the grog of hydration thermal value of cement that has utilized the grog suitable with cement clinker.
The mineral composition of this high reactivity cement grog is counted C with the calculated value based on Bao lattice formula
3s>70%, C
2s<5%, is preferably C
2s<3%.
C
3s is below 70% time, is difficult to obtain to have the equal above high reactivity cement of hydration activity with current short-term strength cement.In addition, according to envrionment conditions, exist neutralisation to suppress to become inadequate worry.
C
2s is 5% when above, and the gap that comprises calcium aluminate and be mineral, amorphous substance etc. tails off mutually, is therefore difficult to sintering high reactivity cement grog or is difficult to use the trade waste that contains a large amount of aluminium components as cement raw materials for sintering.
In addition, in current short-term strength cement, thereby the blending of carrying out cement raw materials for sintering makes the L.S.D. (lime saturation degree) of cement clinker, be below 1, but in high reactivity cement grog of the present invention, L.S.D.>1.By concocting cement raw materials for sintering in the mode of L.S.D.>1, thereby easily obtain C
3s>70%, C
2the high reactivity cement grog of S<5%.
As mentioned above, in high reactivity cement grog of the present invention, L.S.D.>1, therefore contains free lime in cement clinker, but its amount is defined in to 0.5～7.5 % by weight.
Lower than 0.5 % by weight, there is the sintering of high temperature or the position/length variations of sintering zone, the situation of the brick breakage of kiln inside.While exceeding 7.5 % by weight, there is the situation that is caused overplumping by the hydration of the free lime in cement clinker.
High reactivity cement is with SO in above-mentioned high reactivity cement grog
3conversion is counted the mode of 1.5～4.0 % by weight and is added the high reactivity cement that gypsum forms.During lower than 1.5 % by weight, there is the C in cement clinker
3a rapid coagulation, can not guarantee the situation of enough operating times while manufacturing concrete product.While exceeding 4.0 % by weight, exist unreacted gypsum after hardening of cement to cause producing sluggish situation about expanding.
This high reactivity cement, using above-mentioned high reactivity cement grog as parent, therefore has hydration activity more than early strength silicate cement.In addition, be not the cement that meets current cement standard, be therefore difficult to use in the purposes that is necessary for the silicate cement etc. of paying attention to cement standard, if not be can the high cement of widely used versatility like this.
In addition, calcium component is many compared with silica composition, also contains free lime, and it is effective therefore easily producing calcium hydroxide, for neutralisation, suppressing.
More than one the inorganic admixture that neutralisation inhibition type short-term strength cement composition of the present invention is comprised in blast-furnace slag, dehydrated gyp-, limestone micropowder end, volcanic ash material by the above-mentioned high reactivity cement of 60～97 % by weight and 3～40 % by weight forms.
By using above-mentioned high reactivity cement, improve the mixing ratio of this high reactivity cement, even if thereby do not use the chemical additive that comprises various inorganic salt, organic polymer, also can obtain short term strength expression power excellence under short term strength expression power, particularly low temperature, also there is the cement composition of neutralisation rejection.
The inorganic admixture using in the present invention is more than one the inorganic admixture comprising in blast-furnace slag, dehydrated gyp-, limestone micropowder end, volcanic ash material.
Blast-furnace slag is as long as the material for use in blast furnace cement, cement compound, cement composition is all the time not particularly limited.Blast-furnace slag can be used and also can be used in combination with other inorganic admixture with single component.Blast-furnace slag contributes to guarantee mobility, increases longterm strength, suppresses hydration heat, salt resistance.
Dehydrated gyp-is also as long as the material for use in cement compound, cement composition is all the time not particularly limited.Dehydrated gyp-contributes to guarantee mobility, increases short term strength, suppresses to shrink.Dehydrated gyp-is preferably used in combination with other inorganic admixture.
Limestone micropowder end is also as long as the material for use in cement compound, cement composition is all the time not particularly limited.Limestone micropowder end contributes to guarantee mobility, increases short term strength, suppresses to shrink.Limestone micropowder end also preferably and other inorganic admixture be used in combination.
As volcanic ash material, can list the material that silicon ash, metakaolin, activated silica stone flour, diatomite, rice hull ash, atlapulgite, flyash micro mist, flyash meal etc. are used as cement compound all the time.Volcanic ash material contributes to representing intensity, guarantees mobility, suppresses hydration heat.Volcanic ash material can be used and also can be used in combination with other inorganic admixture with single component.
In neutralisation inhibition type short-term strength cement composition of the present invention, the content of high reactivity cement is 60～97 % by weight.
During lower than 60 % by weight (inorganic admixture is more than 40 % by weight), existence can not obtain the situation of the neutralisation under environment that enough intensity maybe can not suppress easily to occur neutralisation under low temperature environment.While exceeding 97 % by weight (inorganic admixture is that 3 % by weight are following), can not obtain fully the effect producing by mixing above-mentioned inorganic admixture, the action effect (such as low-heat, salt resistance, resistance to sulfates etc.) that the mixed cement that is difficult to up till now has, is difficult to be called the material matching with mixed cement.
In the neutralisation inhibition type short-term strength cement composition of the invention described above, the preferred configuration of inorganic admixture has multiple, can use any among them.In following each system, if each constituent material is in following scope, the performance that easily obtain not only having improved strength, neutralisation suppresses, also easily obtains the equal performance of performance (such as low-heat, salt resistance, resistance to sulfates etc.) having with current mixed cement.
< blast-furnace slag-limestone micropowder end is inorganic admixture >
As one of preferred version, there is blast-furnace slag-limestone micropowder end system.This system can be for also wishing to suppress contraction, heating, wishing the situation of inhibition cost etc.Also can realize the effective utilization as the blast-furnace slag of industrial by-products.In this system, aforementioned inorganic admixture consists of blast-furnace slag and limestone micropowder end, and in aforementioned neutralisation inhibition type short-term strength cement composition, the content of aforementioned blast-furnace slag is that the content at 2～39 % by weight, aforementioned limestone micropowder end is 1～10 % by weight.
The content of blast-furnace slag is made as to 2～39 % by weight, is that existence can not obtain the situation of additive effect fully because during lower than 2 % by weight, while exceeding 39 % by weight, and the situation that exists the expression power of short term strength to worsen.
In addition, the content at limestone micropowder end being made as to 1～10 % by weight, is that existence can not obtain the situation of additive effect fully, while exceeding 10 % by weight, exists longterm strength to increase not enough situation because during lower than 1 % by weight.
< blast-furnace slag-limestone micropowder end-dehydrated gyp-is inorganic admixture >
As preferred other one of scheme, there is blast-furnace slag-limestone micropowder end-dehydrated gyp-system.This system is the system that adds dehydrated gyp-in the system of above-mentioned blast-furnace slag-limestone micropowder end.Thereby by adding dehydrated gyp-to increase the generation of ettringite (ettringite), therefore can further improve the early strength expression power under low temperature environment.
This system can be for the manufacture of also wishing to suppress to shrink, also wish the situation of the instant demoulding product that obtains the chemical proofings such as resistance to sulfates etc.In this system, aforementioned inorganic admixture consists of blast-furnace slag, limestone micropowder end and dehydrated gyp-, in aforementioned neutralisation inhibition type short-term strength cement composition, the content of aforementioned blast-furnace slag is that the content at 1～38 % by weight, aforementioned limestone micropowder end is that the content of 1～10 % by weight, aforementioned dehydrated gyp-is 1～5 % by weight.
The content of blast-furnace slag is made as to 1～38 % by weight identical with above-mentioned reason.The content at limestone micropowder end is made as to 1～10 % by weight also identical with above-mentioned reason.It is that existence can not obtain the situation of additive effect fully because during lower than 1 % by weight that the content of dehydrated gyp-is made as to 1～5 % by weight, while exceeding 5 % by weight, occurs producing the sluggish possibility expanding.It should be noted that, the reason that the scope of the Optimum Contents of blast-furnace slag and above-mentioned system depart from is a little owing to further adding dehydrated gyp-.
< blast-furnace slag-volcanic ash material-limestone micropowder end-dehydrated gyp-is inorganic admixture >
As one of preferred other scheme, there is blast-furnace slag-volcanic ash material-limestone micropowder end-dehydrated gyp-system.This system is the system that adds volcanic ash material in above-mentioned blast-furnace slag-limestone micropowder end-dehydrated gyp-system.
This system can be for the manufacture of also wishing to suppress hydration heat, wish to obtain the situation that adds thermomaturation product of high-durability etc.By adding volcanic ash material, because pozzolanic reaction easily generates calcium silicate hydrate (C-S-H), therefore the weather resistance of the so deteriorated principal element of the calcium hydroxide neutralization reaction due to sulfuric acid impregnating is also risen.
Volcanic ash material, as long as be the high material of pozzolanic activity, does not limit, and is preferably flyash.Flyash is industrial by-products, therefore similarly realizes effective utilization with blast-furnace slag, and mobility also rises simultaneously.
Therefore, in this system, aforementioned inorganic admixture consists of blast-furnace slag, volcanic ash material, limestone micropowder end and dehydrated gyp-, the content that in aforementioned neutralisation inhibition type short-term strength cement composition, the content of aforementioned blast-furnace slag is 1～38 % by weight, be 1～38 % by weight, aforementioned limestone micropowder end as the content of the flyash of aforementioned volcanic ash material is that the content of 0.5～5 % by weight, aforementioned dehydrated gyp-is 0.5～5 % by weight.The content of blast-furnace slag is made as to 1～38 % by weight identical with above-mentioned reason.
The content at limestone micropowder end is made as to 0.5～5 % by weight also identical with above-mentioned reason.The content of dehydrated gyp-is made as to 0.5～5 % by weight also identical with above-mentioned reason.The content of flyash is made as to 1～38 % by weight, is that existence can not obtain the situation of additive effect fully because during lower than 1 % by weight, while exceeding 38 % by weight, and the situation that exists the expression power of short term strength to worsen.
It should be noted that, the reason that the Optimum Contents scope at dehydrated gyp-, limestone micropowder end and above-mentioned system depart from is a little in order to adapt with further adding volcanic ash material.
< volcanic ash material is inorganic admixture >
As one of preferred other scheme, there is volcanic ash material system.This system is the most simple system being formed by volcanic ash material single component.This system is used when hope suppresses hydration heat and wishes to obtain high-strength products at an easy rate.
By adding volcanic ash material, because pozzolanic reaction easily generates calcium silicate hydrate (C-S-H), therefore in～expression power of longterm strength is good.In addition, cement is aforementioned high reactivity cement, therefore also can fully guarantee also to have neutralisation rejection by short term strength.Volcanic ash material, as long as be the high material of pozzolanic activity, does not limit the silicon ash that while using with single component, preferred pozzolanic activity is extremely high.
Therefore, in this system, aforementioned inorganic admixture consists of volcanic ash material, in aforementioned neutralisation inhibition type short-term strength cement composition, as the content of the silicon ash of aforementioned volcanic ash material, is 3～15 % by weight.The content of silicon ash is made as when 3～15 % by weight are because exist lower than 3 % by weight and can not obtains fully the situations such as additive effect, while exceeding 15 % by weight, be difficult to guarantee that operability and cost uprise.
< blast-furnace slag-volcanic ash material is inorganic admixture >
As one of preferred other scheme, there is blast-furnace slag-volcanic ash material system.This system is the system that adds blast-furnace slag in above-mentioned volcanic ash material is.This system is used when realizing effective utilization of blast-furnace slag and wishing to obtain high strength at an easy rate.Thereby while using silicon ash as volcanic ash material by adding blast-furnace slag can improve mobility, improve longterm strength and increase, reduce costs.
Therefore, in this system, aforementioned inorganic admixture consists of blast-furnace slag and volcanic ash material, and in aforementioned neutralisation inhibition type short-term strength cement composition, the content of aforementioned blast-furnace slag is 1～38 % by weight, as the content of the silicon ash of aforementioned volcanic ash material, is 2～15 % by weight.The content of blast-furnace slag is made as to 1～38 % by weight identical with above-mentioned reason.
It is also reason same as described above that the content of silicon ash is made as to 2～15 % by weight.It is in order to adapt with further adding blast-furnace slag that the scope of the Optimum Contents of silicon ash and above-mentioned system depart from a little.
< blast-furnace slag-volcanic ash material-dehydrated gyp-is inorganic admixture >
As one of preferred other scheme, there is blast-furnace slag-volcanic ash material-dehydrated gyp-system.This system is the system that adds dehydrated gyp-in above-mentioned blast-furnace slag-volcanic ash material is.This system obtains high-intensityly using while adding thermomaturation product, high-intensity instant demoulding product in hope.
Thereby by the generation that adds dehydrated gyp-ettringite, increase, therefore can further improve the early strength expression power under low temperature environment.Therefore, in this system, aforementioned inorganic admixture consists of blast-furnace slag, volcanic ash material and dehydrated gyp-, the content that in aforementioned neutralisation inhibition type short-term strength cement composition, the content of aforementioned blast-furnace slag is 1～37 % by weight, be 1～15 % by weight, aforementioned dehydrated gyp-as the content of the silicon ash of aforementioned volcanic ash material is 1～9 % by weight.
It is reason same as described above that the content of blast-furnace slag is made as to 1～37 % by weight.It is also reason same as described above that the content of silicon ash is made as to 1～15 % by weight.The content of dehydrated gyp-is made as to 1～9 % by weight, is that existence can not fully obtain the situation of additive effect because during lower than 1 % by weight, while exceeding 9 % by weight, occurs producing the sluggish possibility expanding.The reason that the scope of the Optimum Contents of blast-furnace slag, silicon ash and above-mentioned system depart from is a little in order to adapt with further interpolation dehydrated gyp-.
Inorganic admixture > beyond the above-mentioned system of <
From supply respect, the economic aspect grade of each material, also can make the inorganic admixture of above-mentioned system system in addition.For example, be blast-furnace slag-dehydrated gyp-system, volcanic ash material-dehydrated gyp-system etc.Even if in these systems, the preferable range of the content of each material also with above-mentioned scope same degree.
It should be noted that, the high reactivity cement grog of the high reactivity cement in the invention described above is described above, and mineral composition is counted C with the calculated value based on Bao lattice formula
2s<5%, preferred aforementioned C
2the calculated value based on Bao lattice formula of S is lower than 0% (negative value).Clinker mineral composition based on Bao lattice formula is calculated value, and therefore existing and making calculated value according to condition is negative situation.
In fact there is no content is negative situation, while analyzing with X-ray diffraction, also has the situation that confirms reluctantly peak.In the present invention, C
2the calculated value based on Bao lattice formula of S, lower than 0% (negative value), represents to calculate and does not contain C
2the situation of S.As negative value, for example, it is-4%～-14% left and right.
In addition, also the sulfuric acid in preferred above-mentioned high reactivity cement grog becomes to be divided into SO
3convert meter lower than 1 % by weight.By being made as lower than 1 % by weight, thus the SO in the waste gas while suppressing clinkersintering
xthe generation of (oxysulfide).
the effect of invention
(1), according to neutralisation inhibition type short-term strength cement composition of the present invention, realizing is C in the mineral composition of the calculated value based on Bao lattice formula
3s>70% and C
2in the high reactivity cement grog that S<5% and L.S.D. exceed 1, free lime amount is 0.5～7.5 % by weight, add with SO
3conversion is counted the gypsum of 1.5～4.0 % by weight and effective utilization of " the high reactivity cement " newly developed that forms.In addition, this high reactivity cement is the cement that is not subject to criteria limit, therefore can use trade waste as cement raw materials for sintering, also can have the processing of trade waste concurrently.
(2) for neutralisation inhibition type short-term strength cement composition of the present invention, using high reactivity cement as basis, therefore also have the neutralisation inhibition of the intensity expression power excellence under low temperature environment concurrently, although for being equivalent to the material of mixed cement, have and ordinary Portland cement equal above intensity expression power and neutralisation rejection.In addition, according to the mix proportion mode of this neutralisation inhibition type short-term strength cement composition, also can have the performances such as salt resistance that mixed cement all the time has, resistance to sulfates concurrently, mixed cement that therefore suitable conduct is used in cold district all the time, at the replacement cement that the mixed cement using under the environment of neutralisation easily occurs.
(3) neutralisation inhibition type short-term strength cement composition of the present invention is by high reactivity cement and inorganic admixture (blast-furnace slag, limestone micropowder end, dehydrated gyp-, volcanic ash material) be combined to form, can be according to object, purposes, freely design the system of inorganic admixture, mixing ratio, the mixing ratio of high reactivity cement and inorganic admixture, therefore not only can be under low temperature environment, need under the environment of resistance to neutralisation, can also use the civil construction field of mixed cement all the time, soil/ground field, in the environmental areas such as offal treatment, be widely used.
Embodiment
Below, for neutralisation inhibition type short-term strength cement composition of the present invention, illustrate in greater detail.
Neutralisation inhibition type short-term strength cement composition of the present invention waits " the high reactivity cement " of exploitation in the past to form with inorganic admixture (more than one in blast-furnace slag, dehydrated gyp-, limestone micropowder end, volcanic ash material) by the inventor as previously mentioned.First, for these each materials, describe.
[constituent material]
A. high reactivity cement
The high reactivity cement using in the present invention is the high reactivity cement of the exploitation before the present invention proposes such as inventor, for add the high reactivity cement that gypsum forms in the high reactivity cement grog of developing in the past.Short term strength expression power, in～long-term performance is all good, for neutralisation suppress be effective.
[high reactivity cement grog]
(1) mineral composition
The mineral composition of the high reactivity cement grog using in the present invention is counted C with the calculated value based on Bao lattice formula
3s>70%, C
2s<5%, remains the gap phase for calcium aluminate being main body.
Bao lattice formula is all the time for the host calculating in cement clinker forms the formula of using, and the ratio of each mineral is by the Analysis result calculation of chemical constitution.The ratio obtaining is the calculated value of the analytical results based on chemical constitution just, is not therefore the value consistent with actual ratio in cement clinker.It should be noted that, % is quality %.
[Bao lattice formula]
C
3S(%)＝(4.07×CaO%)-(7.60×SiO
2%)-(6.7×Al
2O
3%)-(1.43×Fe
2O
3%)-(2.85×SO
3%)
C
2S(%)＝(2.8×SiO
2%)-(0.754×C
3S%)
C
3A(%)＝(2.65×Al
2O
3%)-(1.69×Fe
2O
3%)
C
4AF(%)＝3.04×Fe
2O
3%
C
3s is the short length of time to the mineral of main manifestations strength of cement in long-age, and its more intensity is higher and stronger.C
2s less contributes to the performance of intensity in the short length of time, but continues hydration due in long-time, therefore contributes to the intensity performance in long-age, and the gain in strength in the lower and long-age of its more multiple heat is better.In addition chemoresistance, dry shrinkage excellence.
C
3the hydration activity of A is high, significantly contributes to the intensity performance in the short length of time.But when they are many, the gain in strength in solidifying property and long-age worsens soon.In addition, high, the chemoresistance of hydration heating, dry shrinkage are deteriorated.
C
4although AF does not have noticeable feature as hydration performance, when clinkersintering, as gap, contribute to mutually easy-sintering.
In the present invention, be made as C
3s>70% is in order to obtain the high cement of initial stage hydration activity, C
3s is difficult to below 70% time to obtain to have and the high reactivity cement of the equal above hydration activity of current short-term strength cement.The upper limit is not particularly limited, is preferably below 85%.
While exceeding 85%, the situation that exists free lime amount also significantly to increase, can not maintain the stay in grade of cement clinker.In addition, further do not use in a large number the high C of hydration activity
3the mineral of the calcium aluminate systems such as A are due to the intensity performance in considering for a long time, workability, weather resistance etc.
On the other hand, in the present invention, be made as C
2s<5% is in order not have in a substantial change and to obtain the high cement of initial stage hydration activity, C compared with the past clinkersintering condition
2s is 5% when above, by calcium aluminate, is that the gap that mineral, amorphous substance etc. form tails off mutually, is therefore difficult to sintering cement clinker or relatively reduces C
3s amount, is therefore difficult to realize object of the present invention.
Lower value is not particularly limited, and is the calculated value based on Bao lattice formula, C
2s measures as described in above formula, by SiO
2amount and C
3the relation of S amount and determine therefore SiO
2amount less, C
3s measures when many, also causes the situation of calculated value lower than 0 (negative value).In the present invention, also comprise such lower than 0 situation, in order stably to obtain in a large number C
3s is preferably made as lower than 0.
The high reactivity cement grog using in the present invention is except above-mentioned C
3s and C
2beyond S, comprising with calcium aluminate is the gap phase of main body.Gap mutually in, contain C
3a, C
4the mineral such as AF.C
3the content of A preferably counts 4～9% with the calculated value based on above-mentioned Bao lattice formula.In addition C,
4the content of AF is preferably 8～16%.If in this scope, C
3s>70%, C
2the cement clinker of S<5% is easy to stably sintering.Residue is that amorphous gap equates.
(2) sulfuric acid composition
Sulfuric acid composition in the high reactivity cement grog using in the present invention is with SO
3convert meter preferably lower than 1 % by weight.Be 1 % by weight when above, in waste gas, produce SO
x(oxysulfide) or existence are in the inner situation that generates fixed thing and stop up of preheater, therefore not preferred.
(3) free lime
In the high reactivity cement grog using in the present invention, in order further to improve C
3the hydration activity of S preferably contains the free lime for increasing thermal value, raising melting temperature in grog.Its amount is 0.5～7.5 % by weight.During lower than 0.5 % by weight, can not obtain enough effects.While exceeding 7.5 % by weight, cause the reduction of expanding or producing mobility, therefore not preferred.
Then, for the manufacture method of above-mentioned high reactivity cement grog, describe.
(4) manufacture method
The manufacture of the manufacture of above-mentioned high reactivity cement grog and current early-hardening porland cement clinker does not have huge especially variation, to obtain the making cement raw materials for sintering of regulation as C
3s>70%, C
2s<5%, free lime amount are that 0.5～7.5 % by weight and sulfuric acid composition are with SO as far as possible
3the meter that converts is concocted lower than the mode of the cement clinker of 1 % by weight, blending raw material is carried out to sintering in cement kiln etc. and manufacture.
I) cement clinker raw materials for sintering
The Wingdale that all the time uses as grog main raw material, clay, silica, iron material etc. can be same use.In addition, recycling does not have any progress, preferably utilizes to contain with CaO and converts and count the trade waste that is rich in calcium of calcium components more than 20 % by weight.
As containing converting and count the waste of calcium components more than 20 % by weight with CaO, can list the desulfurization slag that utilizes hot metal pretreatment; It is carried out magnetic separation, removes the desulfurization slag of ferrous components; By reduction, process the converter slag of removing ferrous components; The useless building materials of ceramic industry toggle bolt board waste material etc.; Ready mixed concrete mud etc.
Utilize the desulfurization slag of hot metal pretreatment for removing the slag of the sulphur composition in the pig iron, main component is calcium and iron.Also can utilize and screen the many desulfurization slags of calcium of having removed ferrous components with magnetite.Hot metal pretreatment refers to the operation of removing silicon, phosphorus, sulphur for the high purity of iron and steel in the front operation of converter refining.
By reduction, process the LD slag of removing the converter slag of ferrous components and refer to for example following document.Also can utilize this LD slag.
S.Kubodera,T.Koyama,R.Ando?and?R.Kondo,An?Approach?to?the?full?utilization?of?LD?Slag,Transactions?of?The?Iron?and?Steel?Institute?of?Japan,419-427(1979)
Ceramic industry toggle bolt panel material is using cementaceous raw material and cellulose raw material moulding as main raw material, the material that its slaking/sclerosis is formed, there are xylon refinforced cement plate, fiber reinforced cement board, fiber reinforced calcium silicate board etc., as the outer wall finishing material of house and use.
Follow recent house maintenance, house to remove waste material increase, study its processing.Cementaceous part in waste material becomes the cement composition that is rich in calcium, therefore can be as the manufacture raw material of high reactivity cement grog.
Ready mixed concrete mud be the stirrer that is attached to equipment in ready mixed concrete plant, hopper, agitator car etc. concrete, reclaim concrete and concrete cleaning draining is concentrated by reclaiming, the dirt of the state of lost flowability or material dirt is dry and that obtain.
These trade wastes can be used for the part of replace lime stone, clay.To the addition of cement clinker raw materials for sintering according to the difference of the chemical composition of Wingdale and clay and difference is preferably below 400kg in every 1t cement clinker.In every 1t cement clinker, add 400kg when above, have that impurity increases, clinkersintering difficulty, or the quality of obtained cement clinker is produced to dysgenic situation.If trade waste is used for to the part of replace lime stone, also contribute to the reduction of carbon dioxide output, the viewpoint therefore reducing from carrying capacity of environment is preferred.
Ii) raw material blending
Thereby concoct, design the grog that obtains target chemical constitution/mineral composition after sintering, as the above-mentioned each cement clinker raw materials for sintering of benchmark metering, carry out the mixing in co-grinding, the blending bunker in material pulverizing machine.
Above-mentioned blending design is used the coefficient of ratio (modulus) of H.M. (hydraulic index), A.I. (activity coefficient), S.M. (silica modulus), I.M. (iron rate), L.S.D. (lime saturation degree) to carry out samely.Conventionally pay attention to and C
3the growing amount of S has the H.M. of much relations and the S.M. relevant to the easiness of sintering, payes attention to L.S.D. (lime saturation degree) in the present invention.
L.S.D. (lime saturation degree) is to be made as with the calcium oxide content that silicon-dioxide, aluminum oxide, ferric oxide are combined 1.0 index, is shown below.
L.S.D.＝100CaO/(2.80×SiO
2%＋1.18×Al
2O
3%＋0.65Fe
2O
3%)
If L.S.D. below 1, thereby through enough time, can make free lime be made as in the situation of 0%, L.S.D.>1, even if improve sintering temperature, extend sintering time, free lime is also often residual.In common cement clinker, L.S.D. is 0.92～0.96, even if L.S.D. is also 0.94～1.00 in early-hardening porland cement clinker.
L.S.D.>1 in high reactivity cement grog of the present invention.Be made as L.S.D.>1, by concocting cement raw materials for sintering in a small amount of residual mode of free lime, thus can sintering C
3s>70%, C
2the many cement clinkers of calcium component of S<5%.Due to the existence of free lime, initial stage hydration heat uprises, and therefore can make C
3s activation, is also used as exciting agent while mixing with blast-furnace slag.
Higher limit is not particularly limited, and when free lime amount is too much, the stability of grog lacks, and can expand etc., is therefore preferably below 1.16 left and right.
Use in the situation of the coefficient of ratio (modulus) of H.M (hydraulic index), A.I. (activity coefficient), S.M. (silica modulus), I.M. (iron rate) samely, preferably H.M (hydraulic index) is 2.2～2.3 o'clock, S.M. (silica modulus) be 1.7～2.4 and I.M. (iron rate) be 1.0～2.1, H.M (hydraulic index) is lower than 2.1～2.2 o'clock, S.M. (silica modulus) be 1.5～2.0 and I.M. (iron rate) be 0.9～1.4.
Iii) clinkersintering
The high reactivity cement grog using in the present invention is the cement raw materials for sintering of concocting by above-mentioned raw materials to be utilized cement sintering oven and early-hardening porland cement clinker sintering in the past similarly to operate to carry out sintering obtain.If a small amount of sintering can be also electric furnace sintering.
Sintering temperature is preferably 1250～1600 ℃.During lower than 1250 ℃, C
3the generation of S self is impossible.In addition,, while exceeding 1600 ℃, the refractory body dissolving of rotary kiln inside etc. hinder the sintering of cement clinker.Clinker cooling after sintering, fragmentation etc. are same.
[high reactivity cement]
The high reactivity cement using in the present invention is with SO in above-mentioned high reactivity cement grog
3conversion is counted the mode of 1.5～4.0 % by weight and is added gypsum, and the middle co-grindings such as precision work pulverizing mill that coexist with grinding aid one obtain.Operation, device are identical with the finishing step in cement manufacture in the past.The material that gypsum is used in also manufacturing with cement in the past with grinding aid is identical.
The amount of the gypsum adding is with SO
31.5～4.0 % by weight are counted in conversion.During lower than 1.5 % by weight, there is the C in cement clinker
3when A rapid coagulation, manufacture concrete product etc., can not guarantee the situation of enough operating times.While exceeding 4.0 % by weight, exist after hardening of cement because unreacted gypsum causes producing sluggish situation about expanding.Fines content is not particularly limited, preferably with Brian value, counts 3000cm
2more than/g.
The fines content of early strength silicate cement is in the past large, high-performance water reducing agent is difficult to onset, therefore in order to obtain the mobility of regulation, must improve the amount that water compares or increase a little high-performance water reducing agent, but the hydration activity of the above-mentioned high reactivity cement using in the present invention is high, more than early strength silicate cement in the past, therefore do not need to increase fines content as early strength silicate cement in the past, in addition, even if increase, also the hydration rapidly such as free lime while contacting with water, at particle surface, form hydrate layer, even if therefore water is not needed above or does not increase the amount of high-performance water reducing agent than bringing up to, also can obtain the mobility of regulation.
B. inorganic admixture
(a) blast-furnace slag
Blast-furnace slag for iron processed blast furnace manufacture the by product producing during the pig iron, together with the pig iron with the molten state of approximately 1500 ℃ after blast furnace takes out, the sand-like amorphous body that water-cooled is solidified is pulverized the material forming, and is caused the material with latent hydraulicity of hydration reaction by alkali-activator.As long as for material and the Brian value used in blast furnace cement, cement compound are 1500cm all the time
2material more than/g, quality is not particularly limited, and preferably meets the material at JIS A6206:1997 " the reinforcement of concrete blast-furnace cinder micro-powder end ".Blast-furnace slag contributes to guarantee mobility, suppresses hydration heat, increases longterm strength, salt resistance etc.
(b) limestone micropowder end
Limestone micropowder end comprises calcium carbonate, and purity is as long as for common obtainable Wingdale, can be used no problemly.As long as for the material using in cement, cement composition, cement compound all the time, also preferred from supply respect, economic aspect.Limestone micropowder end is carried out as required classification by crushed limestone and is manufactured, and Brian specific surface area is preferably 2000～10000cm
2/ g.Lower than 2000cm
2during/g, can not obtain the additive effect at limestone micropowder end.Exceed 1000cm
2during/g, according to the difference of content, mobility variation while cost is also uprised.Limestone micropowder end contributes to guarantee mobility, increases short term strength, suppresses to shrink.
(c) dehydrated gyp-
As dehydrated gyp-, the dehydrated gyp-that has natural dehydrated gyp-, hydrofluoric acid dehydrated gyp-, natural 2 water gypsum, by-product 2 water gypsum or the 2 water gypsum sintering that reclaim from waste gypsum plate are manufactured etc., as long as for the gypsum that contains 90% above dehydrated gyp-, all can use.In addition, the fines content of dehydrated gyp-is not particularly limited, with Brian value, counts 3000～8000cm
2/ g, be preferably 4000～6000cm
2/ g.Dehydrated gyp-mainly contains and helps improve short term strength, but to guaranteeing mobility, suppressing to shrink and also work.
(d) volcanic ash material
Volcanic ash material refers to be rich in to have under the existence of water and Ca (OH)
2or Ca ionic reaction and generate new hydrate response characteristic (pozzolanic reaction characteristic) be rich in SiO
2, Al
2o
3inorganic substance, can list silicon ash, metakaolin, activated silica stone flour, diatomite, rice hull ash, atlapulgite, flyash micro mist, flyash meal etc.(above-mentioned blast-furnace slag is also counted as the one of volcanic ash material, but in so-called volcanic ash material, does not contain blast-furnace slag in the present invention.)
Wherein, utilize arc type electric furnace etc., the by product silicon ash containing in waste gas when finishing metal silicon, ferrosilicon has high pozzolanic reaction characteristic, also contribute to effective utilization of by product, therefore as high strength material, use in a large number, even if also preferably use silicon ash as volcanic ash material in the present invention all the time.
Silicon ash, as long as be the material of use in cement compound etc. all the time, to being not particularly limited in quality, preferably meets the material of JIS A6207:2000 " the reinforcement of concrete silicon ash ".Volcanic ash material contributes to intensity performance, and the rising to weather resistance, hydration heat suppress also to work.
Then, for the coordinating example of the neutralisation inhibition type short-term strength cement composition of the present invention that uses above-mentioned each material, describe.
[coordinating example]
Neutralisation inhibition type short-term strength cement composition of the present invention is in above-mentioned high reactivity cement, to mix more than one the inorganic admixture comprising in above-mentioned blast-furnace slag, above-mentioned limestone micropowder end, above-mentioned dehydrated gyp-and above-mentioned volcanic ash material to form.
This neutralisation inhibition type short-term strength cement composition must at least contain high reactivity cement more than 60 % by weight and contain inorganic admixtures more than 3 % by weight.High reactivity cement is during lower than 60 % by weight, and the present invention is difficult to obtain that target strength is improved, neutralisation suppresses.That is, can not obtain having and the material that is equivalent to mixed cement of ordinary Portland cement equality strength expression power and neutralisation rejection.
In addition, inorganic admixture is during lower than 3 % by weight, be difficult to obtain the action effect of the above-mentioned each material that forms inorganic admixture, not only be difficult to obtain improved strength, neutralisation inhibition, and be difficult to obtain the equal performance of performance (such as low-heat, salt resistance, resistance to sulfates etc.) having with mixed cement in the past, be difficult to be referred to as and the similar material of mixed cement.
As mentioned above, volcanic ash material can be used separately, also can be used in combination with blast-furnace slag, limestone micropowder end, dehydrated gyp-, two modes all can, but blast-furnace slag, limestone micropowder end, dehydrated gyp-preferably at least with other two kinds in any number of being used in combination.
This be due to, as mentioned above, short～longterm strength performance that volcanic ash material significantly contributes to, even if therefore also easily realize object of the present invention for single component, although at least a portion single component of blast-furnace slag, limestone micropowder end, dehydrated gyp-contribute to short～longterm strength performance can not obtain enough effects.
Neutralisation inhibition type short-term strength cement composition of the present invention is as long as for meeting the material of above-mentioned condition, consider the viewpoints such as material supply, waste material utilization, cost, and inorganic admixture can be made various systems.
As preferred system, be (1) blast-furnace slag-limestone micropowder end system, (2) blast-furnace slag-limestone micropowder end-dehydrated gyp-system, (3) blast-furnace slag-limestone micropowder end-dehydrated gyp--volcanic ash material system, (4) volcanic ash material system, (5) blast-furnace slag-volcanic ash material system, (6) blast-furnace slag-volcanic ash material-dehydrated gyp-system.
If these systems not only can realize the raising of improved strength, neutralisation inhibition, and easily maintain the action effect that mixed cement in the past has.The use-pattern of each neutralisation inhibition type short-term strength cement composition of the inorganic admixture of these (1)～(6) as previously mentioned.
[inorganic admixture]
(1) blast-furnace slag-limestone micropowder end system
The suitable cooperation of blast-furnace slag-limestone micropowder end system is: in neutralisation inhibition type short-term strength cement composition, the content of aforementioned blast-furnace slag is that the content at 2～39 % by weight, aforementioned limestone micropowder end is 1～10 % by weight.Carry out such cooperation as previously mentioned.
(2) blast-furnace slag-limestone micropowder end-dehydrated gyp-system
The suitable cooperation of blast-furnace slag-limestone micropowder end-dehydrated gyp-system is: in neutralisation inhibition type short-term strength cement composition, the content of aforementioned blast-furnace slag is that the content at 1～38 % by weight, aforementioned limestone micropowder end is that the content of 1～10 % by weight, aforementioned dehydrated gyp-is 1～5 % by weight.Carry out such cooperation as previously mentioned.
(3) blast-furnace slag-limestone micropowder end-dehydrated gyp--volcanic ash material system
With the suitable material of blast-furnace slag-limestone micropowder end-dehydrated gyp--volcanic ash material system with coordinate and be: in neutralisation inhibition type short-term strength cement composition, the content of aforementioned blast-furnace slag is 1～38 % by weight, the content that is 1～38 % by weight, aforementioned limestone micropowder end as the content of the flyash of aforementioned volcanic ash material is that the content of 0.5～5 % by weight, aforementioned dehydrated gyp-is 0.5～5 % by weight.Such material and cooperation are as previously mentioned.
(4) volcanic ash material system
Suitable material and the cooperation of volcanic ash material system are: the content as the silicon ash of aforementioned volcanic ash material in neutralisation inhibition type short-term strength cement composition is 3～15 % by weight.Such material and cooperation are as previously mentioned.
(5) blast-furnace slag-volcanic ash material system
Suitable material and the cooperation of blast-furnace slag-volcanic ash material system are: in neutralisation inhibition type short-term strength cement composition, the content of aforementioned blast-furnace slag is 1～38 % by weight, as the content of the silicon ash of aforementioned volcanic ash material, is 2～15 % by weight.Such material and cooperation are as previously mentioned.
(6) blast-furnace slag-volcanic ash material-dehydrated gyp-system
Suitable material and the cooperation of blast-furnace slag-volcanic ash material-dehydrated gyp-system are: in neutralisation inhibition type short-term strength cement composition, the content of aforementioned blast-furnace slag is 1～37 % by weight, as the content of the silicon ash of aforementioned volcanic ash material, being 1～15 % by weight, aforementioned dehydrated gyp-, content is 1～9 % by weight.Such material and cooperation are as previously mentioned.
Then, for the manufacture method of neutralisation inhibition type short-term strength cement composition of the present invention, describe.
[manufacture of neutralisation inhibition type short-term strength cement composition]
The mixing equipment of manufacture mixed cement in the past can be suitably used in the manufacture of neutralisation inhibition type short-term strength cement composition of the present invention.In addition, can be in growing concrete factory etc. when concrete is manufactured by measure respectively high reactivity cement and inorganic be Additive manufacture.
Then, for the performance validation tests of neutralisation inhibition type short-term strength cement composition of the present invention, describe.
[performance validation tests of neutralisation inhibition type short-term strength cement composition]
The object of the present invention is to provide intensity expression power, particularly the short term strength expression power excellence under low temperature environment as previously mentioned, also there is the neutralisation inhibition type short-term strength cement composition of neutralisation inhibition.
At this, the compressive strength of accelerating at neutralisation test and 10 ℃ and 20 ℃ is tested.
< is used material >
(1) cement
1) high reactivity cement
By having adjusted the industrial raw material such as Wingdale, clay, become cement raw materials for sintering sintering at 1450 ℃ of the composition of regulation, thereby manufacture C
3s is 72% and C
2s is 1%, L.S.D. is 1.02, free lime amount is the high reactivity cement grog of 2.5 % by weight, adds wherein with SO
3the dihydrate gypsum of 3.0 % by weight is counted in conversion, obtains manufacturing experimently high reactivity cement.The actual machine of cement factory is all used in manufacture from material process to finishing step.
2) (Taiheiyo Cement Corporation manufactures ordinary Portland cement; Relatively use)
(2) inorganic admixture
1) blast-furnace cinder micro-powder end (DC CO., the Cerament of LTD.; Brian value 4470cm
2/ g)
2) limestone micropowder end (Zhi Fu Pacific Ocean company manufacture; Brian value 10240cm
2/ g)
3) dehydrated gyp-(DC CO., LTD. manufacture; Brian value 3840cm
2/ g)
4) volcanic ash material
Flyash (EPD Co., Ltd.'s manufacture)
Silicon ash (Egyptian producing)
5) sand
Based on the standard sand of JIS R5201 " physical test of cement "
The cooperation > of < cement composition
Each cooperation of the cement composition in neutralisation inhibition type short-term strength cement composition of the present invention and comparative example shown in table 1.
[table 1]
The mixing ratio of cement composition
Above-mentioned each cement composition is that each constituent material V-Mixer that regulation is coordinated is obtained by mixing.
The blending of < mortar and mixing >
Blending and the compounding process of the blending of mortar and the mixing mortar based on recording in JIS R5201 " physical test method of cement " carry out.It should be noted that, all regard cement composition as cement and concoct.
< accelerates neutralisation test >
The mortar of making by aforesaid method is accelerated to neutralisation based on JIS A1153 " concrete acceleration neutralisation test method ", measure and accelerate neutralization depth.Measure the length of time be made as 1 week, 4 weeks, 8 weeks.
< compressive strength test >
The mortar sample of 4 × 4 × 16cm that the mortar that use utilizes aforesaid method to make forms, the compressive strength test method based on recording in JIS R5201 " physical test method of cement " is carried out.Wherein, test be made as 3 days the length of time, 7 days, 28 days.In addition under 2 kinds of curing temperatures of 10 ℃ and 20 ℃, carry out to the slaking of testing the length of time.
In addition, in the short length of time (3 days, 7 days), in order to observe the impact of curing temperature on intensity expression power, the ratio of the intensity at the intensity at having obtained 10 ℃ and 20 ℃ " volume efficiency=(compressive strength/20 at 10 ℃ ℃ at compressive strength) × 100 ".
< result >
In the result of accelerating neutralisation test shown in table 2.In addition the result of testing in compressive strength shown in table 3.
[table 2]
Accelerate neutralisation test-results
From above-mentioned table 2, embodiment is with compared with the comparative example can not being called the comparative example No.2 that is equivalent to mixed cement, and acceleration neutralization depth is little.Even if it is also little particularly to accelerate neutralization depth compared with being equivalent to the comparative example No.4 of comparative example No.3, ordinary Portland cement single component of mixed cement of blast furnace cement.
Therefore, neutralisation inhibition type short-term strength cement composition of the present invention can be called: although for the similar cement composition of mixed cement in the past, compared with mixed cement in the past neutralisation rejection high, have and the cement composition of ordinary Portland cement neutralisation rejection on an equal basis above.
[table 3]
Compressive strength test-results
From above-mentioned table 3, embodiment is all good with comparative example phase specific tenacity expression power.Even if also good with the comparative example No.4 phase specific tenacity expression power of comparative example No.3, ordinary Portland cement single component of mixed cement that is equivalent to blast furnace cement, particularly the difference of the short term strength in the 3 days length of time is also large.Volume efficiency is preferably more than 75%, embodiment is all high, is more than 75%.
In addition, from except the kind of cement, the cooperation No.9 of same cooperation and No.10, cooperation No.15 and No.16, cooperation No.23 and No.24, cooperation No.28 and No.29 respectively relatively, while using high reactivity cement, intensity expression power is good, and particularly the short term strength under 10 ℃ of such low temperature environments significantly improves.
Neutralisation inhibition type short-term strength cement composition of the present invention can be called: although for the similar cement composition of mixed cement in the past, with mixed cement phase specific tenacity expression power in the past well, particularly the short term strength under low temperature environment improves, has and the cement composition of ordinary Portland cement intensity expression power on an equal basis above.
Claims (7)
1. a neutralisation inhibition type short-term strength cement composition, is characterized in that, it comprises 60～97 % by weight high reactivity cement and 3～40 % by weight inorganic admixtures, and described high reactivity cement is to be C in the mineral composition of the calculated value based on Bao lattice formula
3s>70% and C
2in the high reactivity cement grog that S<5% and L.S.D. exceed 1, free lime amount is 0.5～7.5 % by weight, add with SO
3the gypsum that 1.5～4.0 % by weight are counted in conversion forms, and described inorganic admixture comprises more than one in blast-furnace slag, dehydrated gyp-, limestone micropowder end, volcanic ash material.
2. neutralisation inhibition type short-term strength cement composition according to claim 1, it is characterized in that, described inorganic admixture consists of blast-furnace slag and limestone micropowder end, in described neutralisation inhibition type short-term strength cement composition, the content of described blast-furnace slag is that the content at 2～39 % by weight, described limestone micropowder end is 1～10 % by weight.
3. neutralisation inhibition type short-term strength cement composition according to claim 1, it is characterized in that, described inorganic admixture consists of blast-furnace slag, limestone micropowder end and dehydrated gyp-, in described neutralisation inhibition type short-term strength cement composition, the content of described blast-furnace slag is that the content at 1～38 % by weight, described limestone micropowder end is that the content of 1～10 % by weight, described dehydrated gyp-is 1～5 % by weight.
4. neutralisation inhibition type short-term strength cement composition according to claim 1, it is characterized in that, described inorganic admixture consists of blast-furnace slag, volcanic ash material, limestone micropowder end and dehydrated gyp-, the content that in described neutralisation inhibition type short-term strength cement composition, the content of described blast-furnace slag is 1～38 % by weight, be 1～38 % by weight, described limestone micropowder end as the content of the flyash of described volcanic ash material is that the content of 0.5～5 % by weight, described dehydrated gyp-is 0.5～5 % by weight.
5. neutralisation inhibition type short-term strength cement composition according to claim 1, it is characterized in that, described inorganic admixture consists of volcanic ash material, in described neutralisation inhibition type short-term strength cement composition, as the content of the silicon ash of described volcanic ash material, is 3～15 % by weight.
6. neutralisation inhibition type short-term strength cement composition according to claim 1, it is characterized in that, described inorganic admixture consists of blast-furnace slag and volcanic ash material, in described neutralisation inhibition type short-term strength cement composition, the content of described blast-furnace slag is 1～38 % by weight, as the content of the silicon ash of described volcanic ash material, is 2～15 % by weight.
7. neutralisation inhibition type short-term strength cement composition according to claim 1, it is characterized in that, described inorganic admixture consists of blast-furnace slag, volcanic ash material and dehydrated gyp-, the content that in described neutralisation inhibition type short-term strength cement composition, the content of described blast-furnace slag is 1～37 % by weight, be 1～15 % by weight, described dehydrated gyp-as the content of the silicon ash of described volcanic ash material is 1～9 % by weight.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-185663 | 2011-08-29 | ||
| JP2011185663A JP5818579B2 (en) | 2011-08-29 | 2011-08-29 | Neutralization suppression type early strong cement composition |
| PCT/JP2012/051513 WO2013031246A1 (en) | 2011-08-29 | 2012-01-25 | Neutralization-preventive high-early-strength cement composition |
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| KR (1) | KR101617695B1 (en) |
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| CN109180050A (en) * | 2018-10-23 | 2019-01-11 | 何纪萱 | A kind of sandy soil rock powder delay outer-penetrating agent |
| CN114080372A (en) * | 2020-03-27 | 2022-02-22 | 住友大阪水泥股份有限公司 | Cement clinker and cement composition |
| CN115702127A (en) * | 2020-06-18 | 2023-02-14 | 大成建设株式会社 | Hydraulic composition, hydraulic composition mixture, and cured product |
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| JP6166153B2 (en) * | 2013-11-08 | 2017-07-19 | 株式会社デイ・シイ | Ground improvement material |
| JP6264644B2 (en) * | 2014-01-28 | 2018-01-24 | 住友大阪セメント株式会社 | Admixture, cement composition and hardened cement |
| KR101725283B1 (en) * | 2015-07-06 | 2017-04-10 | 주식회사 포스코건설 | Composition for concrete comprising siliceous dust and composition method using the same thing |
| JP6676355B2 (en) * | 2015-12-07 | 2020-04-08 | 株式会社トクヤマ | Hydraulic composition |
| JP6579977B2 (en) * | 2016-02-29 | 2019-09-25 | 株式会社デイ・シイ | Cement composition |
| JP6629632B2 (en) * | 2016-02-29 | 2020-01-15 | 株式会社デイ・シイ | Fly ash cement composition |
| JP6965484B2 (en) * | 2017-09-11 | 2021-11-10 | 株式会社ピーエス三菱 | Manufacturing method of high-strength concrete and high-strength concrete |
| CN108191338A (en) * | 2018-01-24 | 2018-06-22 | 暨南大学 | A kind of high-performance artificial sand concrete prepared by the use of mountain flour and rice hull ash as admixture |
| JP7219785B2 (en) * | 2021-03-30 | 2023-02-08 | Ｕｂｅ三菱セメント株式会社 | Mixed cement composition and manufacturing method thereof |
| WO2023171770A1 (en) * | 2022-03-10 | 2023-09-14 | デンカ株式会社 | Cement composition |
| CN114751668B (en) * | 2022-04-06 | 2023-01-31 | 盐城市鼎力新材料有限公司 | Early-strength ultrafine mineral admixture and preparation method thereof |
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| US4774064A (en) * | 1986-12-23 | 1988-09-27 | Mississippi Chemical Corporation | Conversion of calcium compounds into solid and gaseous compounds |
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| JP2010037371A (en) | 2008-08-01 | 2010-02-18 | Ube Ind Ltd | Cement-based solidification material for suppressing heavy-metal elution and solidification treatment method |
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| JP5446752B2 (en) * | 2009-11-11 | 2014-03-19 | 宇部興産株式会社 | Mixed cement clinker and method for producing the same |
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| 候贵华等: "高硅酸三钙硅酸盐水泥熟料组成及性能的研究", 《硅酸盐学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180050A (en) * | 2018-10-23 | 2019-01-11 | 何纪萱 | A kind of sandy soil rock powder delay outer-penetrating agent |
| CN114080372A (en) * | 2020-03-27 | 2022-02-22 | 住友大阪水泥股份有限公司 | Cement clinker and cement composition |
| CN114080372B (en) * | 2020-03-27 | 2022-11-15 | 住友大阪水泥股份有限公司 | Cement clinker and cement composition |
| CN115702127A (en) * | 2020-06-18 | 2023-02-14 | 大成建设株式会社 | Hydraulic composition, hydraulic composition mixture, and cured product |
Also Published As
| Publication number | Publication date |
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| JP2013047153A (en) | 2013-03-07 |
| JP5818579B2 (en) | 2015-11-18 |
| CN103764588B (en) | 2015-09-09 |
| KR101617695B1 (en) | 2016-05-03 |
| WO2013031246A1 (en) | 2013-03-07 |
| KR20140043493A (en) | 2014-04-09 |
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